Dye nitrates

ABSTRACT

Nitrates of triarylmethane dyes useful in printing inks, pastes for ball point pens, inks, copying papers, transparent coatings, etc.

United States Patent 1151 3,682,979 Tartter et al. 1 Aug. 8, 1972 [54]DYE NITRATES [72] Inventors: Arnold Tartter, Lambsheim; [56] Referencesand ga i N s g r i UNITED STATES PATENTS f gg a 0 3,535,347 10/1970Bitterli ..260/393 731 Assignee: Badische Anilin- & Soda-Fabrik Ak-OTHER PUBLICATIONS gin g Ludwigshafenl Moeller, Inorganic Chemistry,1952, pp. 463-464.

me, ermany 22 Filed; May 1 1970 Primary Examiner-Lewis Gotts AssistantExaminer-R. S. Weissberg [21] Appl. NO- 38,515 Attorney-Johnston, Root,OKeeffe, Keil, Thompson & Shurtleff [30] Foreign Application PriorityData 57] ABSTRACT May 1969 Germany 19 25 Nitrates of triarylmethane dyesuseful in printing inks, U S Cl 260/393 pastes for ball point pens,inks, copying papers, trans- 51 Int. Cl. ..C09b 11/12 parent coatmgs[58] Field of Search ..260/393 1 Claim, N0 Drawings DYE NITRATES Theinvention relates to the dyes having the formulae (l) and (Il):

and their use for the production of printing inks, pastes for ball pointpens, copying papers, hectographic papers, stamping and other inks andtransparent coatings.

The new dyes may be prepared for example by double decomposition or byreaction of the Rhodulin dye base with nitric acid.

The dyes known under the names RHODULIN BLUE 6G or SETOGLAUCIN (C. l. 42025, cation of formula (1)) and RHODULIN BLUE B" or SETOCYANlNE 0" (C.l. 42 I40, cation of formula (II)) are hydrochloric acid salts of2"-chloro-4,4- bisdimethylaminotriphenylcarbinol and 2"-chloro-3,3'-bismethyl-4,4'-bisethylaminotriphenylcarbinol. It is advantageous touse these chlorides, which may also be present in the form of doublesalts with zinc chloride, or another soluble salt as the startingmaterial for the production of the nitrates. Examples of water-solublenitrates which are suitable for double decomposition with the RHODULINdye salts are the alkali metal nitrates or alkaline earth metal nitratessuch as sodium nitrate, potassium nitrate or calcium nitrate, orammonium nitrate.

, In the reaction of RHODULIN dye bases with nitric acid, the latter ispreferably used as a dilute acid. It may also be advantageous to-addnitric acid in the double decomposition of RHODULIN dye salts withnitrates.

The new dyes are distinguished by very good solubility in organicsolvents such as alcohols, glycols and glycol ethers. .They aretherefore eminently suitable for the production of copying papers,hectographic papers, stamping, marking and other inks, transparentcoatings, and particularly for printing inks such as glycol andflexographic printing inks, and pastes for ball point pens. It is alsopossible to use them together with spirit-soluble binders, for examplein transparent coatings.

Products prepared with the dye nitrates are surprisingly very much lesscorrosive than products prepared with the commercial chlorides or thezinc chloride double salts described in the literature. The low tendencyto corrosion is important where the dye will come into contact withmetals.

As compared with the commercial chlorides, the new nitrates moreoverhave the advantageous property of crystallizing better and more rapidly.This makes possible a less troublesome and more rapid production ofRHODULIN BLUE and permits better utilization of capacity because in thesynthesis the basic dye is isolated direct as the nitrate. The nitratesare moreover in a concentrated form and practically devoid of salt andare soluble in organic solvents without any residue. The problem ofwaste disposal which is otherwise very critical in the case of dyes iseasier to solve because of the low water-solubility of the nitrates.

The invention is illustrated by the following examples in which partsand percentages are by weight unless otherwise specified.

EXAMPLE I ly or after cooling by filtration or suction filtration. 86

parts of RHODULIN BLUE 6G nitrate of the formula (1) above is thusobtained.

EXAMPLE 2 140 parts of RHODULIN BLUE 6G concentrated in the form of thesalt-containing hydrochloric acid salt is dissolved in 2,200 parts ofwater at 60 C. While stirring, a solution of 44 parts of sodium nitratein 1,000 parts of water is gradually added. The dye, which at first isin a somewhat gelatinous form, crystallizes completely in a sort time atto C'and after only about one hour can be cooled and isolated. The dyemay be suction filtered very easily and rapidly and can be suckedpractically dry on the suction filter so that afterdrying by heating canbe dispensed with. The yield of the bronzy, green glistening RHODULINBLUE 6G nitrate is about 100 parts.

RHODULlN 5B (hydrochloride) can be converted into the correspondingnitrate of the formula (II) above in an analogous manner.

EXAMPLE 3 130 parts of RHODULIN BLUE 6G zinc chloride double salt isstirred in 2,000 parts of water and 250 parts of 25 percent ammoniasolution for 2 hours at room temperature, then for an hour while heatingat 60 C and is then allowed to cool. The dye base obtained is suctionfiltered and washed with dilute ammonia solution until it is freed fromzinc. The base is then suspended in 3,000 parts of water at to C and 64parts of 32.5 percent nitric acid is added so that a pH of 1.7 isachieved; the hot solution is filtered and allowed to cool. Thedeposited crystals are suction filtered, washed with water and dried.parts of particularly pure RHODULIN BLUE 6G nitrate having hightinctorial strength is obtained.

We claim:

1. A dye selected from the class consisting of dyes having theformulas:-

